CN113527848A - Wormwood powder shoe material and preparation method thereof - Google Patents
Wormwood powder shoe material and preparation method thereof Download PDFInfo
- Publication number
- CN113527848A CN113527848A CN202110918586.XA CN202110918586A CN113527848A CN 113527848 A CN113527848 A CN 113527848A CN 202110918586 A CN202110918586 A CN 202110918586A CN 113527848 A CN113527848 A CN 113527848A
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- CN
- China
- Prior art keywords
- shoe material
- wormwood powder
- antioxidant
- polyester prepolymer
- temperature
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 93
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 235000003261 Artemisia vulgaris Nutrition 0.000 title claims abstract description 58
- 235000009051 Ambrosia paniculata var. peruviana Nutrition 0.000 title claims abstract description 57
- 235000003097 Artemisia absinthium Nutrition 0.000 title claims abstract description 57
- 240000001851 Artemisia dracunculus Species 0.000 title claims abstract description 57
- 235000017731 Artemisia dracunculus ssp. dracunculus Nutrition 0.000 title claims abstract description 57
- 239000001138 artemisia absinthium Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims description 32
- 229920000728 polyester Polymers 0.000 claims abstract description 89
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 38
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 18
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 14
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000010010 raising Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000005187 foaming Methods 0.000 claims description 25
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000806 elastomer Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 12
- 230000004224 protection Effects 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000001384 succinic acid Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 8
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 229920000180 alkyd Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- -1 neodymium dodecylbenzenesulfonate Chemical compound 0.000 claims description 3
- SIINVGJQWZKNSJ-UHFFFAOYSA-K neodymium(3+);octadecanoate Chemical compound [Nd+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SIINVGJQWZKNSJ-UHFFFAOYSA-K 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004890 Hydrophobing Agent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000013016 damping Methods 0.000 description 4
- 239000002781 deodorant agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 208000003251 Pruritus Diseases 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical group CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 201000004624 Dermatitis Diseases 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 208000010668 atopic eczema Diseases 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000004054 inflammatory process Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000007803 itching Effects 0.000 description 2
- 238000007719 peel strength test Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 208000002474 Tinea Diseases 0.000 description 1
- 241000130764 Tinea Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 210000002683 foot Anatomy 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 201000004647 tinea pedis Diseases 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/0009—Footwear characterised by the material made at least partially of alveolar or honeycomb material
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/14—Footwear characterised by the material made of plastics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2203/18—Binary blends of expanding agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention particularly relates to a wormwood powder shoe material which comprises the following raw materials in parts by weight: 5-20 parts of polyester prepolymer A, 30-50 parts of polyester prepolymer B, 15-35 parts of ethylene-vinyl acetate copolymer, 4-10 parts of wormwood powder, 2-7 parts of chain extender, 0.5-3 parts of carbon black, 0.6-3 parts of hydrophobing agent, 0.7-2.2 parts of antioxidant, 0.6-5 parts of cross-linking agent and 0.8-3.5 parts of composite foaming agent.
Description
Technical Field
The invention relates to the technical field of shoe materials, and particularly relates to a wormwood powder shoe material and a preparation method thereof.
Background
In recent years, rapid development of the shoe making industry also promotes continuous development of shoe sole materials, foamed shoe soles gradually replace shoe sole materials such as PVC and rubber, and the like, and main foamed shoe soles at the present stage are PE, EVA, SBS and PU, wherein the PE foamed shoe soles have good wear resistance and heat insulation, but are weak in skid resistance and easy to deform; the EVA foaming sole has good elasticity, strong shock resistance and weather resistance but low mechanical strength; SBS foamed sole need cooperate with other high polymer to modify, such as TPR sole material that it makes has anti-skidding, ventilative characteristic, but the price is relatively higher; the PU foaming sole is small in density, high in strength and good in elasticity, can be adjusted in a targeted mode according to specific needs, can show the characteristics of flame retardance, static resistance, hydrolysis resistance, hydrophobic oil drainage and the like after treatment, can meet different requirements of various shoes, and is an ideal sole material. However, shoes are easy to wear and deform in the long-time wearing process, bacteria are easy to breed and peculiar smell is easy to generate in the humid environment, and feet are easy to grow eczema, tinea pedis and the like.
Mugwort as one of the traditional medicinal plants in China is widely applied to various medicines and health-care products. The folium Artemisiae Argyi has effects of eliminating dampness, relieving itching, inhibiting bacteria, and resisting inflammation when used externally, and can be used for treating skin pruritus, skin tinea, eczema, etc. According to the invention, the wormwood powder is applied to the sole material to prepare the health-care functional shoe material with the functions of inhibiting fungus and germs, removing peculiar smell, resisting inflammation and relieving itching, so that the shoe material becomes the sole material with health-care function and practicability.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide the wormwood powder shoe material which is light in texture, flexible, stretch-resistant, good in rebound and shock absorption performance, not easy to absorb water, has bacteriostatic and deodorant effects, is a degradable material and does not pollute the environment after being used.
The invention also aims to provide the wormwood powder shoe material and the preparation method thereof, the preparation method has simple process, controllable conditions, low cost and high production efficiency, and the prepared product has stable quality.
The purpose of the invention is realized by the following technical scheme:
the wormwood powder shoe material comprises the following raw materials in parts by weight:
the wormwood powder shoe material has good mechanical property, rebound resilience and shock absorption performance and moderate hardness by using the polyester prepolymer and the ethylene-vinyl acetate copolymer as raw materials, and has good antibacterial and deodorant effects by adding wormwood powder. Wherein, the water absorption of the shoe material is reduced by adding the hydrophobic agent; the composite foaming agent has a good micropore foaming effect, and the pores are uniformly and compactly distributed, so that the shoe material is low in density, good in elasticity and good in air permeability; the compound use of the antioxidant enables the shoe material to have better oxidation resistance and light stability, and can avoid thermal oxidation degradation in the preparation process of the shoe material; the carbon black plays a role of a reinforcing agent in the invention, improves the wear resistance, ultraviolet resistance and heat-resistant stability of the shoe material, and simultaneously is also used as a pigment, so that the prepared shoe material has good color.
Preferably, the preparation of the polyester prepolymer A comprises the following steps: weighing 1, 4-butanediol and succinic acid with the molar ratio of 1.0-1.2:1, uniformly mixing, raising the temperature to 160-180 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 1-2h, adding a catalyst A and an antioxidant A, continuously raising the temperature to 200-220 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa for carrying out polycondensation reaction for 3-6h, and stopping the reaction to obtain the polyester prepolymer A.
Preferably, the preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the alkyd molar ratio of 1.0-1.3:1, uniformly mixing the short-chain dihydric alcohol and aliphatic saturated dibasic acid, raising the temperature to 160-180 ℃ under the protection of normal pressure nitrogen, stirring and reacting for 1-2h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 200-220 ℃ until almost no water is distilled out, gradually reducing the pressure to below 5kPa for polycondensation reaction for 3-7h, and stopping the reaction to obtain the polyester prepolymer B.
Preferably, the short-chain diol is at least two of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol, and the aliphatic saturated diacid is at least two of succinic acid, glutaric acid, adipic acid, pimelic acid and sebacic acid.
Preferably, the catalyst A and the catalyst B are at least one of p-toluenesulfonic acid, neodymium stearate, neodymium dodecylbenzenesulfonate or tetraisopropyl titanate.
Preferably, the antioxidant A and the antioxidant B are both at least one of the antioxidant 168 and the antioxidant 1010. More preferably, the antioxidant A and the antioxidant B are both a composition of the antioxidant 168 and the antioxidant 1010 with the mass ratio of 1: 0.8-1.2.
Preferably, the number average molecular weight of the polyester prepolymer A is 6000-10000g/mol, and the number average molecular weight of the polyester prepolymer B is 7500-13000 g/mol.
The polyester prepolymer A prepared by using 1, 4-butanediol and succinic acid as raw materials by adopting a melt polycondensation method has regular molecular chains, stronger crystallization capacity and better strength; the polyester prepolymer B prepared from short-chain dihydric alcohol and aliphatic saturated dibasic acid is amorphous hydroxyl-terminated aliphatic saturated copolyester, and has high flexibility. In the preparation process of the prepolymer, the control of the reaction temperature is particularly important, when the reaction temperature is too low, the activity of the reaction monomer is small, the molecular weight is slowly increased, and when the reaction temperature is too high, the side reaction is easily aggravated. Therefore, the two-stage heating in the preparation of the prepolymer is a step-type heating mode, and the reaction process can be better controlled. The catalyst A and the catalyst B selected by the invention have the advantages of low price, low toxicity, no heavy metal pollution, no oxidability and good catalytic effect, and the antioxidant 168 and the antioxidant 1010 are compounded to generate a synergistic effect, so that the polyester can be effectively prevented from being oxidized for a long time. Moreover, the molecular weight of the polyester prepolymer A and the polyester prepolymer B is related to the molecular weight and the mechanical property of the prepared polyester elastomer, and the higher the molecular weight of the polyester prepolymer A is, the higher the hardness of the prepared polyester elastomer is; when the molecular weight of the polyester prepolymer B is increased, the chain extension efficiency is high, the tensile strength and the elongation at break of the prepared polyester elastomer are improved, and the prepared polyester elastomer has better rebound resilience and heat-resistant stability, so that the invention limits the molecular weight of the prepolymer to obtain the wormwood powder shoe material with high flexibility and comfort level and good damping rebound resilience.
Preferably, the chain extender is at least one of diphenylmethane diisocyanate, p-phenylene diisocyanate and naphthalene diisocyanate.
The chain extender adopted by the invention is diisocyanate chain extender which has higher reaction activity, the-NCO group in the chain extender reacts with the-OH group in the prepolymer to generate polyester elastomer with larger molecular weight, and the molar ratio of the-NCO group to the-OH group is preferably 1.1-1.2 in the invention in order to ensure the chain extension reaction to be complete.
Preferably, the composite foaming agent is at least one or two of sodium bicarbonate, p-toluenesulfonyl hydrazide, azobisisobutyronitrile and diisopropyl azodicarboxylate. As a more preferable scheme of the invention, the composite foaming agent is p-toluenesulfonyl hydrazide and diisopropyl azodicarboxylate in a mass ratio of 1: 0.4-0.6 of the mixed composition.
Preferably, the hydrophobic agent is octafluoropentanol, the crosslinking agent is dicumyl peroxide or trimethylolpropane, and the antioxidant is a composition formed by mixing antioxidant BHT, antioxidant 1010 and UV531 according to the mass ratio of 1:1: 0.4.
The composite foaming agent has a good micropore foaming effect, and the foam holes are uniformly and densely distributed, so that the shoe material is low in density, good in elasticity and good in air permeability. Through the compound use of the antioxidant, the shoe material has better oxidation resistance and light stability, and can avoid thermal oxidation degradation in the preparation process of the shoe material. In addition, in order to improve the water absorption of the material, octafluoropentanol is selected as a hydrophobic agent, has low surface free energy and is migrated to the surface of the material, so that the hydrophobicity of the shoe material can be effectively improved, and the water absorption of the shoe material is effectively reduced.
The other purpose of the invention is realized by the following technical scheme: a preparation method of the wormwood powder shoe material comprises the following preparation steps:
(1) drying the dried folium artemisiae argyi in a drying oven at the temperature of 75-85 ℃ for 3-6h, grinding the dried folium artemisiae argyi by a grinder after cooling, and filtering impurities and particles in the folium artemisiae argyi powder by a filtering device to obtain the folium artemisiae argyi powder with the particle size of 190-mesh 210 meshes for later use;
(2) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 140-150 ℃ under the condition of nitrogen, uniformly stirring the two, adding the chain extender for three times, mixing and stirring, and gradually reducing the pressure to below 5kPa for reaction for 2-6 hours to obtain the polyester elastomer;
(3) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the weight parts, and mechanically blending to obtain a mixed material;
(4) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 70-80 ℃, and feeding the mixed material into a granulator for granulation to obtain granules;
(5) and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 160-180 ℃, and the foaming time is 5-10 min.
The wormwood powder shoe material is prepared by the method, the preparation method is simple and controllable, the production efficiency is high, the wormwood powder shoe material is clean and environment-friendly, the production cost is low, and the prepared product is stable in quality and high in production efficiency. The prepared shoe material has good antibacterial and deodorant effects by adding the wormwood powder, and has the characteristics of flexibility, stretch resistance, good rebound and shock absorption performance, strong hydrophobicity and hydrolysis resistance by using the polyester elastomer and the ethylene-vinyl acetate copolymer as raw materials, and wastes after use can be naturally degraded without causing pollution to the environment. In the step (2), the control of the reaction temperature is important, the polyester prepolymer A is completely melted at a temperature of more than 120 ℃ and is fully mixed and dispersed with the polyester prepolymer B, the chain extension reaction efficiency is improved along with the increase of the temperature, the molecular weight is gradually increased, but when the temperature exceeds 150 ℃, the chain extender can be self-polymerized, so that the temperature is limited to 140 ℃ and 150 ℃ in the step (2), and the chain extender is added in portions.
The invention has the beneficial effects that: the polyester foaming material prepared from the polyester prepolymer and the ethylene-vinyl acetate copolymer has good mechanical property, rebound resilience and shock absorption performance and moderate hardness, and the prepared shoe material has good antibacterial and deodorant effects by adding the wormwood powder. The raw materials are matched with each other, the compatibility is good, and the water absorption of the shoe material is reduced by adding the hydrophobic agent; the composite foaming agent has a good micropore foaming effect, and the pores are uniformly and compactly distributed, so that the shoe material is low in density, good in elasticity and good in air permeability; the compound use of the antioxidant enables the shoe material to have better oxidation resistance and light stability, and can avoid thermal oxidation degradation in the preparation process of the shoe material; the carbon black plays a role of a reinforcing agent in the invention, improves the wear resistance, ultraviolet resistance and heat-resistant stability of the shoe material, and simultaneously is also used as a pigment, so that the prepared shoe material has good color. Moreover, the shoe material has the advantages of simple preparation process, controllable conditions, low cost, high production efficiency and stable quality of the prepared product.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The wormwood powder shoe material comprises the following raw materials in parts by weight:
in this embodiment, the preparation of the polyester prepolymer a comprises the following steps: weighing 1, 4-butanediol and succinic acid with a molar ratio of 1.0:1, uniformly mixing, raising the temperature to 160 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 1h, adding a catalyst A and an antioxidant A, continuously raising the temperature to 200 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa, carrying out polycondensation reaction for 3h, and stopping the reaction to obtain the polyester prepolymer A.
The preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the molar ratio of alkyd being 1.0:1 and aliphatic saturated dibasic acid, uniformly mixing, raising the temperature to 160 ℃ under the protection of normal pressure nitrogen, stirring for reaction for 1h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 200 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa, carrying out polycondensation reaction for 3h, and stopping the reaction to obtain the polyester prepolymer B.
The short-chain dihydric alcohol is a mixture of ethylene glycol and 1, 4-butanediol in a mass ratio of 1:1, and the aliphatic saturated dibasic acid is a mixture of succinic acid and adipic acid in a mass ratio of 1: 2.
The catalyst A and the catalyst B are p-toluenesulfonic acid.
The antioxidant A and the antioxidant B are both a composition formed by mixing an antioxidant 168 and an antioxidant 1010 according to a mass ratio of 1: 0.8.
The number average molecular weight of the polyester prepolymer A is 6000g/mol, and the number average molecular weight of the polyester prepolymer B is 7500 g/mol.
The chain extender is diphenylmethane diisocyanate.
The composite foaming agent is composed of sodium bicarbonate and p-toluenesulfonyl hydrazide in a mass ratio of 2:1.
The wormwood powder shoe material is prepared by the following preparation steps:
(1) drying the dried folium artemisiae argyi in a 75 ℃ oven for 3h, grinding the dried folium artemisiae argyi by a grinder after cooling, and filtering impurities and particles in the folium artemisiae argyi powder by a filtering device to obtain the folium artemisiae argyi powder with the particle size of 190 meshes;
(2) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 140 ℃ under the condition of nitrogen, uniformly stirring the polyester prepolymer A and the polyester prepolymer B, adding the chain extender for three times, mixing and stirring, and then gradually reducing the pressure to be below 5kPa for reaction for 2 hours to obtain the polyester elastomer;
(3) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the weight parts, and mechanically blending to obtain a mixed material;
(4) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 70 ℃, and sending the mixed material into a granulator for granulation to obtain granules;
(5) and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 160 ℃, and the foaming time is 5 min.
Example 2
The wormwood powder shoe material comprises the following raw materials in parts by weight:
in this embodiment, the preparation of the polyester prepolymer a comprises the following steps: weighing 1, 4-butanediol and succinic acid with a molar ratio of 1.1:1, uniformly mixing, raising the temperature to 170 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 1.5h, adding a catalyst A and an antioxidant A, continuously raising the temperature to 210 ℃ until almost no water is distilled out, gradually reducing the pressure to below 5kPa, carrying out polycondensation reaction for 4h, and stopping the reaction to obtain the polyester prepolymer A.
The preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the molar ratio of alkyd being 1.1:1, uniformly mixing the short-chain dihydric alcohol and aliphatic saturated dibasic acid, raising the temperature to 160-180 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 1.5h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 210 ℃ until almost no water is distilled out, gradually reducing the pressure to below 5kPa for polycondensation for 5h, and stopping the reaction to obtain the polyester prepolymer B.
The short-chain dihydric alcohol is a mixture of 1, 3-propylene glycol and 1, 4-butanediol in a mass ratio of 1:1, and the aliphatic saturated dibasic acid is a mixture of succinic acid and sebacic acid in a mass ratio of 2:1.
The catalyst A and the catalyst B are neodymium dodecylbenzene sulfonate.
The antioxidant A and the antioxidant B are both a composition formed by mixing an antioxidant 168 and an antioxidant 1010 according to a mass ratio of 1:1.
The number average molecular weight of the polyester prepolymer A is 7000g/mol, and the number average molecular weight of the polyester prepolymer B is 9000 g/mol.
The chain extender is naphthalene diisocyanate.
The composite foaming agent is composed of p-toluenesulfonyl hydrazide and azobisisobutyronitrile in a mass ratio of 1.2: 0.9.
The wormwood powder shoe material is prepared by the following preparation steps:
(1) drying the dried folium artemisiae argyi in an oven at 80 ℃ for 4h, grinding the dried folium artemisiae argyi by using a grinder after cooling, and filtering impurities and particles in the folium artemisiae argyi powder by using a filtering device to obtain folium artemisiae argyi powder with the particle size of 200 meshes;
(2) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 140 ℃ under the condition of nitrogen, uniformly stirring the polyester prepolymer A and the polyester prepolymer B, adding the chain extender for three times, mixing and stirring, and gradually reducing the pressure to below 5kPa for reaction for 2-6 hours to obtain the polyester elastomer;
(3) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the weight parts, and mechanically blending to obtain a mixed material;
(4) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 70 ℃, and sending the mixed material into a granulator for granulation to obtain granules;
(5) and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 170 ℃, and the foaming time is 7 min.
Example 3
The wormwood powder shoe material comprises the following raw materials in parts by weight:
in this embodiment, the preparation of the polyester prepolymer a comprises the following steps: weighing 1, 4-butanediol and succinic acid with a molar ratio of 1.1:1, uniformly mixing, raising the temperature to 180 ℃ under the protection of normal pressure nitrogen, stirring for reaction for 1h, adding a catalyst A and an antioxidant A, continuously raising the temperature to 200-220 ℃ until almost no water is distilled out, gradually reducing the pressure to below 5kPa for polycondensation reaction for 5h, and stopping the reaction to obtain the polyester prepolymer A.
The preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the molar ratio of alkyd being 1.2:1 and aliphatic saturated dibasic acid, uniformly mixing, raising the temperature to 180 ℃ under the protection of normal pressure nitrogen, stirring for reaction for 1h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 210 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa for polycondensation reaction for 5h, and stopping the reaction to obtain the polyester prepolymer B.
The short-chain dihydric alcohol is a mixture of 1, 3-propylene glycol and 1, 4-butanediol in a mass ratio of 1:1, and the aliphatic saturated dibasic acid is a mixture of succinic acid, adipic acid and sebacic acid in a mass ratio of 1:1: 1.
And the catalyst A and the catalyst B are neodymium stearate.
The antioxidant A and the antioxidant B are both a composition formed by mixing an antioxidant 168 and an antioxidant 1010 according to a mass ratio of 1:1.
The number average molecular weight of the polyester prepolymer A is 8000g/mol, and the number average molecular weight of the polyester prepolymer B is 9000 g/mol.
The chain extender is diphenylmethane diisocyanate.
The composite foaming agent is composed of p-toluenesulfonyl hydrazide and diisopropyl azodicarboxylate in a mass ratio of 1.5: 1.2.
The wormwood powder shoe material is prepared by the following preparation steps:
(1) drying the dried folium artemisiae argyi in an oven at 80 ℃ for 5 hours, cooling, grinding by using a grinder, and filtering impurities and particles in the folium artemisiae argyi powder by using a filtering device to obtain folium artemisiae argyi powder with the particle size of 200 meshes;
(2) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 140 ℃ under the condition of nitrogen, uniformly stirring the polyester prepolymer A and the polyester prepolymer B, adding the chain extender for three times, mixing and stirring, and gradually reducing the pressure to be below 5kPa for 5 hours to obtain the polyester elastomer;
(3) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the weight parts, and mechanically blending to obtain a mixed material;
(4) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 80 ℃, and sending the mixed material into a granulator for granulation to obtain granules;
(5) and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 170 ℃, and the foaming time is 8 min.
Example 4
The wormwood powder shoe material comprises the following raw materials in parts by weight:
in this embodiment, the preparation of the polyester prepolymer a comprises the following steps: weighing 1, 4-butanediol and succinic acid with a molar ratio of 1.2:1, uniformly mixing, raising the temperature to 180 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 2 hours, adding a catalyst A and an antioxidant A, continuously raising the temperature to 220 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa, carrying out polycondensation reaction for 6 hours, and stopping the reaction to obtain the polyester prepolymer A.
The preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the molar ratio of alkyd being 1.3:1 and aliphatic saturated dibasic acid, uniformly mixing, raising the temperature to 180 ℃ under the protection of normal pressure nitrogen, stirring for reaction for 2h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 220 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa, carrying out polycondensation reaction for 6h, and stopping the reaction to obtain the polyester prepolymer B.
The short-chain dihydric alcohol is 1, 2-pentanediol, and the aliphatic saturated dibasic acid is a mixture of succinic acid, adipic acid and sebacic acid in a mass ratio of 2:1: 1.
The catalyst A and the catalyst B are both tetraisopropyl titanate.
The antioxidant A and the antioxidant B are both compositions formed by mixing the antioxidant 168 and the antioxidant 1010 according to the mass ratio of 1: 1.2.
The number average molecular weight of the polyester prepolymer A is 10000g/mol, and the number average molecular weight of the polyester prepolymer B is 12000 g/mol.
The chain extender is p-phenylene diisocyanate.
The composite foaming agent is composed of p-toluenesulfonyl hydrazide and azobisisobutyronitrile in a mass ratio of 2: 1.2.
The wormwood powder shoe material is prepared by the following preparation steps:
(6) drying the dried folium artemisiae argyi in an oven at 85 ℃ for 6 hours, grinding the dried folium artemisiae argyi by using a grinder after cooling, and filtering impurities and particles in the folium artemisiae argyi powder by using a filtering device to obtain folium artemisiae argyi powder with the particle size of 210 meshes;
(7) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 150 ℃ under the condition of nitrogen, uniformly stirring the polyester prepolymer A and the polyester prepolymer B, adding the chain extender for three times, mixing and stirring, and gradually reducing the pressure to be below 5kPa for reaction for 6 hours to obtain the polyester elastomer;
(8) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the weight parts, and mechanically blending to obtain a mixed material;
(9) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 80 ℃, and sending the mixed material into a granulator for granulation to obtain granules;
and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 180 ℃, and the foaming time is 10 min.
Comparative example 1
Comparative example 1 differs from example 2 in that: comparative example 1 no ethylene vinyl acetate copolymer was added.
Comparative example 2
Comparative example 2 differs from example 3 in that: this comparative example 2 uses a commercially available blowing agent AC instead of the composite blowing agent of example 3.
Comparative example 3
Comparative example 3 differs from example 3 in that: this comparative example 3 uses a commercially available TPU resin BT65AR in place of the polyester elastomer obtained in step (2) of example 3.
The wormwood powder shoe materials prepared in the examples 1-4 and the comparative examples 1-3 are subjected to various physical property tests, and the hardness test is carried out according to GB/T531.1-2008 standard; the tensile strength and the elongation at break are tested according to the GB/T531.1-2008 standard; the peel strength test was carried out by cutting the moxa powder shoe material prepared in examples 1 to 4 and degree ratios 1 to 3 into sample pieces, and testing the pieces with a universal tester (AI-7000-MT, high-speed rail technologies, Inc.); the hydrolysis performance test is to place the obtained wormwood powder shoe material into a sodium hydroxide solution with the concentration of 10%, place the wormwood powder shoe material for 24 hours, take out the wormwood powder shoe material, clean and dry the wormwood powder shoe material, and test and record data according to a peel strength test method; the damping performance is tested by adopting the GB/T30907-2014 standard; the antibacterial performance is tested by adopting an antibacterial mildew-proof plastic mildew-proof grade test method (1999). The results of the performance tests of the above examples 1 to 4 and comparative examples 1 to 3 are shown in the following table 1.
TABLE 1 tables of Performance test data for examples 1-4 and comparative examples 1-3
As can be seen from the comparison of the data table 1, the wormwood powder shoe materials prepared in the examples 1-4 all show good mechanical properties, hydrolysis resistance and antibacterial ability. Compared with the example 2, the wormwood powder shoe material prepared in the comparative example 1 has obviously reduced tensile strength, elongation at break and damping performance, and the peel strength and hydrolysis performance are far inferior to those of the wormwood powder shoe material prepared in the example 2, which shows that the elasticity, toughness and water resistance of the material are obviously improved by adding the ethylene-vinyl acetate copolymer, so that the prepared shoe material has good mechanical property, damping buffer and water resistance. Compared with the example 3, the relative reduction of the peel strength, the elongation at break, the hydrolytic property and the shock absorption performance of the wormwood powder prepared in the comparative example 2 and the comparative example 3 is obvious, which shows that the composite foaming agent adopted in the example 3 has good foaming effect, so that the wormwood powder shoe material has low hardness, good elasticity and strong toughness.
The above specific examples are further illustrative of the technical solutions and advantages of the present invention, and are not intended to limit the embodiments. It will be apparent to those skilled in the art that any obvious alternative is within the scope of the invention without departing from the inventive concept.
Claims (10)
1. A wormwood powder shoe material is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the wormwood powder shoe material as claimed in claim 1, wherein: the preparation method of the polyester prepolymer A comprises the following steps: weighing 1, 4-butanediol and succinic acid with the molar ratio of 1.0-1.2:1, uniformly mixing, raising the temperature to 160-180 ℃ under the protection of normal pressure nitrogen, stirring for reacting for 1-2h, adding a catalyst A and an antioxidant A, continuously raising the temperature to 200-220 ℃ until almost no water is distilled off, gradually reducing the pressure to below 5kPa for carrying out polycondensation reaction for 3-6h, and stopping the reaction to obtain the polyester prepolymer A.
3. The wormwood powder shoe material as claimed in claim 1, wherein: the preparation of the polyester prepolymer B comprises the following steps: weighing short-chain dihydric alcohol with the alkyd molar ratio of 1.0-1.3:1, uniformly mixing the short-chain dihydric alcohol and aliphatic saturated dibasic acid, raising the temperature to 160-180 ℃ under the protection of normal pressure nitrogen, stirring and reacting for 1-2h, adding a catalyst B and an antioxidant B, continuously raising the temperature to 200-220 ℃ until almost no water is distilled out, gradually reducing the pressure to below 5kPa for polycondensation reaction for 3-7h, and stopping the reaction to obtain the polyester prepolymer B.
4. The wormwood powder shoe material as claimed in claim 3, wherein: the short-chain dihydric alcohol is at least two of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol, and the aliphatic saturated dibasic acid is at least two of succinic acid, glutaric acid, adipic acid, pimelic acid and sebacic acid.
5. The wormwood powder shoe material as claimed in claim 2 or 3, wherein: the catalyst A and the catalyst B are at least one of p-toluenesulfonic acid, neodymium stearate, neodymium dodecylbenzenesulfonate or tetraisopropyl titanate.
6. The wormwood powder shoe material as claimed in claim 2 or 3, wherein: the antioxidant A and the antioxidant B are both at least one of antioxidant 168 and antioxidant 1010.
7. The wormwood powder shoe material as claimed in claim 1, wherein: the number average molecular weight of the polyester prepolymer A is 6000-10000g/mol, and the number average molecular weight of the polyester prepolymer B is 7500-13000 g/mol.
8. The wormwood powder shoe material as claimed in claim 1, wherein: the chain extender is at least one of diphenylmethane diisocyanate, p-phenylene diisocyanate and naphthalene diisocyanate.
9. The wormwood powder shoe material as claimed in claim 1, wherein: the composite foaming agent is at least one of sodium bicarbonate, p-toluenesulfonyl hydrazide, azobisisobutyronitrile and diisopropyl azodicarboxylate.
10. The method for producing a wormwood powder shoe material as claimed in any one of claims 1 to 9, characterized in that: the preparation method comprises the following preparation steps:
(1) drying the dried folium artemisiae argyi in a 75-85 ℃ oven, cooling, grinding by using a grinder, and filtering impurities and particles in the folium artemisiae argyi powder by using a filtering device to obtain the folium artemisiae argyi powder for later use;
(2) weighing the polyester prepolymer A and the polyester prepolymer B according to the weight parts, mixing and stirring, raising the temperature to 140-150 ℃ under the condition of nitrogen, uniformly stirring the two, adding the chain extender for three times, mixing and stirring, and gradually reducing the pressure to below 5kPa for reaction for 2-6 hours to obtain the polyester elastomer;
(3) weighing the polyester elastomer prepared in the step (2), the ethylene-vinyl acetate copolymer, the wormwood powder, the carbon black and the crosslinking agent according to the parts by weight, and mechanically blending to obtain a mixed material;
(4) adding an antioxidant, a hydrophobic agent and a composite foaming agent into the mixture obtained in the step (3) for mixing, controlling the mixing temperature at 70-80 ℃, and feeding the mixed material into a granulator for granulation to obtain granules;
(5) and (5) placing the granules obtained in the step (4) into a mold coated with stearic acid for mold pressing foaming to obtain the wormwood powder shoe material, wherein the foaming temperature is 160-180 ℃, and the foaming time is 5-10 min.
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| CN114835971A (en) * | 2022-05-20 | 2022-08-02 | 中国皮革制鞋研究院有限公司 | High-elasticity and breathable wormwood powder foaming composite material and preparation method and application thereof |
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Application publication date: 20211022 |